WO2021066488A1 - Polypropylene-based composite material - Google Patents

Abstract

The present invention relates to a polypropylene-based composite material comprising: (A) polypropylene; and (B) an olefin-based polymer satisfying the requirements of: (1) a melt index (MI, 190°C and 2.16 kg load conditions) of 0.1-10.0 g/10 min; (2) a melting temperature of 20-70°C as measured by differential scanning calorimetry (DSC); and (3) high-temperature melting peaks being confirmed at 75-150°C, as measured by a differential scanning calorimetry precision measurement method (SSA), in which the sum of melting enthalpies, ΔH (75), in the corresponding region is 1.0 J/g or more. The polypropylene-based composite material of the present invention can exhibit excellent impact strength.

Description

Polypropylene composite

[Mutual citation with related application]

This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0121151 filed on September 30, 2019, and all contents disclosed in the documents of the Korean patent application are included as part of this specification.

The present invention relates to a polypropylene-based composite, and more particularly, to a polypropylene-based composite having improved impact strength and mechanical properties, including a low-density olefin-based polymer exhibiting high mechanical stiffness by introducing a high crystallinity region.

In general, a composition for automobile interior and exterior parts has been used as a polypropylene resin composition containing an impact reinforcing material and an inorganic filler based on polypropylene (PP).

Until the mid-1990s, before the development of an ethylene-α-olefin copolymer polymerized by applying a metallocene catalyst, it was used as a material for automobile interior and exterior materials, especially bumper covers. Most polypropylene resin compositions were used as EPR (Ethylene Propylene Rubber) or EPDM. (ethylene propylene diene rubber) was mainly used as an impact reinforcing material. However, since the advent of the ethylene-α-olefin copolymer synthesized by a metallocene catalyst, an ethylene-α-olefin copolymer has begun to be used as an impact reinforcing material, and is now the mainstream. This is because the polypropylene-based composite material using this has balanced physical properties such as impact strength, elastic modulus, and flexural strength, has good moldability, and has many advantages such as low price.

Polyolefins such as ethylene-α-olefin copolymers synthesized by a metallocene catalyst have a narrow molecular weight distribution and good mechanical properties because their molecular structure is more uniformly controlled than that of a Ziegler-Natta catalyst. Low-density ethylene elastomers polymerized by a metallocene catalyst are also relatively uniformly inserted into the polyethylene (PE) molecule than that of the Ziegler-Natta catalyst. It also has good properties.

However, there is a limit to securing impact resistance according to various usage environments, and development of a polypropylene-based composite material capable of overcoming such limitations is required.

The problem to be solved by the present invention is to provide a polypropylene-based composite material that can exhibit remarkably improved impact strength properties with excellent mechanical strength.

In order to solve the above problems, the present invention provides a polypropylene-based composite material comprising (A) polypropylene, and (B) an olefin-based polymer satisfying the requirements of the following (1) to (3).

(1) The melt index (Melt Index, MI, 190°C, 2.16 kg load condition) is 0.1 g/10 minutes to 10.0 g/10 minutes, and (2) The melting temperature is 20° C. to 70 when measured with a differential scanning calorimeter (DSC). ℃, and (3) a differential scanning calorimeter precision measurement method (SSA), a high-temperature melting peak is observed at 75°C to 150°C, and the total ΔH(75) of the melting enthalpy of the corresponding region is 1.0 J/g or more.

The polypropylene-based composite according to the present invention contains an olefin-based polymer that can be uniformly dispersed in the composite due to its excellent compatibility with polypropylene while exhibiting high mechanical stiffness due to the introduction of a high crystallinity region, so that no additional additives are used. It can exhibit remarkably improved impact strength properties with excellent mechanical strength without the need.

1 is a graph showing the results of measuring the melting temperature of the polymer of Preparation Example 1 using a differential scanning calorimeter (DSC).

2 is a graph showing the results of measuring the melting temperature of the polymer of Comparative Preparation Example 1 using a differential scanning calorimeter (DSC).

3 is a graph showing the result of measuring the total ΔH (75) of the melting enthalpy at 75° C. to 150° C. by differential scanning calorimetry precision measurement (SSA) for the polymer of Preparation Example 1. FIG.

FIG. 4 is a graph showing the result of measuring the total ΔH (75) of melting enthalpy at 75° C. to 150° C. for the polymer of Comparative Preparation Example 1 by differential scanning calorimeter precision measurement (SSA).

Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.

The terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

In the present specification, the term "polymer" means a polymer compound prepared by polymerization of monomers of the same or different types. The generic term "polymer" includes the terms "homopolymer", "copolymer", "terpolymer" as well as "interpolymer". In addition, the "interpolymer" refers to a polymer prepared by polymerization of two or more different types of monomers. The generic term "interpolymer" refers not only to the term "copolymer" (usually used to refer to polymers made from two different monomers), as well as to polymers (made from three different types of monomers, typically As used) the term “terpolymer”. This includes polymers made by polymerization of four or more types of monomers.

Typically, polypropylene is used as an interior and exterior material for automobiles such as automobile bumpers, and polyolefin-based polymers are used together as an impact reinforcing material to compensate for the low impact strength of polypropylene. Among these, low-density polyolefin-based polymers are used to exhibit properties such as impact resistance, elastic modulus, and tensile properties according to various use environments and to have high impact strength properties.However, in this case, the problem of lowering the strength of polypropylene is rather there was.

On the other hand, in the present invention, when manufacturing a polypropylene-based composite material, by using an olefin-based polymer that exhibits excellent impact strength improvement effect and can be uniformly dispersed in the composite due to excellent miscibility with polypropylene, it is excellent without using additional additives. It can exhibit significantly improved impact strength properties along with mechanical strength.

The polypropylene-based composite material according to the present invention contains (A) polypropylene and (B) an olefin-based polymer satisfying the requirements of the following (1) to (3).

(1) The melt index (Melt Index, MI, 190°C, 2.16 kg load condition) is 0.1 g/10 minutes to 10.0 g/10 minutes, and (2) The melting temperature is 20° C. to 70 when measured with a differential scanning calorimeter (DSC). ℃, and (3) a differential scanning calorimeter precision measurement method (SSA), a high-temperature melting peak is observed at 75°C to 150°C, and the total ΔH(75) of the melting enthalpy of the corresponding region is 1.0 J/g or more.

Hereinafter, each component will be described in detail.

(A) polypropylene

In the polypropylene-based composite material according to an embodiment of the present invention, the polypropylene may be specifically a polypropylene homopolymer or a copolymer of propylene and an alpha-olefin monomer, wherein the copolymer is alternating ( alternating) or random, or block copolymers. However, in the present invention, the polypropylene is a compound that can be overlapped with the olefin polymer is excluded, and is a different compound from the olefin polymer.

The alpha-olefin-based monomer may specifically be an aliphatic olefin having 2 to 12 carbon atoms or 2 to 8 carbon atoms. More specifically, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1- Octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-itocene, 4,4-dimethyl-1-pentene, 4,4- Diethyl-1-hexene or 3,4-dimethyl-1-hexene, and the like, and any one or a mixture of two or more of them may be used.

More specifically, the polypropylene may be any one or a mixture of two or more selected from the group consisting of a polypropylene copolymer, a propylene-alpha-olefin copolymer, and a propylene-ethylene-alpha-olefin copolymer. The coalescence can be a random or block copolymer.

In addition, the polypropylene has a melt index (MI) of 0.5 g/10min to 100 g/10min, measured at 230°C and a load of 2.16kg, specifically, the melt index (MI) is 1 g/10min to 90 g/ It may be 10 min, more specifically 10 g/10min to 50 g/10min. If the melt index of polypropylene is out of the above range, there is a concern that a problem may occur during injection molding.

Specifically, in the polypropylene-based composite material according to an embodiment of the present invention, the polypropylene has a melt index (MI) measured at 230°C and a load of 2.16 kg from 0.5 g/10min to 100 g/10min, specifically It may be an impact copolymer of 1 g/10min to 90 g/10min, and more specifically, a propylene-ethylene impact copolymer, and the impact copolymer is 50 weight based on the total weight of the polypropylene-based composite % To 90% by weight, more specifically 80% to 90% by weight may be included. When the impact copolymer having such physical properties is included as polypropylene in the above content range, strength properties, particularly low temperature strength properties, can be improved.

The above-described impact copolymer may be prepared to satisfy the above-described physical property requirements using a conventional polymer preparation reaction, or may be obtained and used commercially. As a specific example, SEETE™ M1600 manufactured by LG Chemical Co., and the like can be mentioned.

In addition, in the polypropylene-based composite material according to an embodiment of the present invention, the polypropylene is specifically measured at a DSC melting point in the range of 120°C to 160°C, and a load condition of 230°C and 2.16kg according to ASTM-D 1238. , It may be one or more random propylene copolymers having a melt flow rate (MFR) in the range of 5 g/10min to 120 g/10min, wherein the random propylene copolymer is 75% to 97% by weight based on the total weight of the polypropylene-based composite , More specifically, it may be included in 85% by weight to 91% by weight. When the polypropylene having such physical properties is included in the above content range, the mechanical strength of the polypropylene composite, such as hardness, can be improved. The random propylene copolymer may be prepared to satisfy the above-described physical property requirements using a conventional polymer preparation reaction, or may be obtained and used commercially. As a specific example, Braskem™ PP R7021-50RNA of Braskem America Inc. or Formolene™ 7320A of Formosa Plastics Corporation of the United States may be mentioned.

(B) Olefin polymer

The olefin-based polymer included in the polypropylene-based composite according to the present invention has an ultra-low density, and a high crystalline region is introduced compared to the conventional olefin-based polymer, so that the density and melt index (Melt Index, MI, 190°C) are the same. , 2.16 kg load condition), it shows higher tensile strength and tear strength. The olefin-based polymer included in the polypropylene-based composite material according to the present invention is prepared by a production method comprising the step of polymerizing an olefin-based monomer by introducing hydrogen gas in the presence of a polymerization catalyst composition. Depending on the input, a highly crystalline region is introduced to show excellent mechanical stiffness.

The melt index (MI) can be adjusted by adjusting the amount of the catalyst used in the process of polymerizing the olefin-based polymer to the comonomer, and affects the mechanical properties, impact strength, and moldability of the olefin-based polymer. In the present specification, the melt index is measured at 190° C., 2.16 kg load condition according to ASTM D1238 in a low density condition of 0.850 g/cc to 0.890 g/cc, and 0.1 g/10 minutes to 10 g/10 minutes And specifically, 0.3 g/10 minutes to 9 g/10 minutes, more specifically 0.4 g/10 minutes to 7 g/10 minutes.

When measuring a differential scanning calorimeter (DSC), the melting point (Tm) may be 20°C to 70°C, specifically 20°C to 60°C, and more specifically 25°C to 50°C.

When measuring the differential scanning calorimeter precision measurement (SSA), a high-temperature melting peak is found at 75°C to 150°C, and specifically, the region may be 75°C to 145°C, and more specifically 75°C to 135°C. At this time, the total ΔH (75) of the melting enthalpy of the corresponding region is 1.0 J/g or more, specifically 1.0 J/g to 3.0 J/g, and more specifically 1.0 J/g to 2.0 J/g. have.

In general, the melting temperature (Tm) measurement using a differential scanning calorimeter (DSC) is a temperature that is approximately 30°C lower than the glass transition temperature (Tg) after heating at a constant rate to a temperature approximately 30°C higher than the melting temperature (Tm). After the first cycle of cooling at a constant rate until, the peak of the standard melting temperature (Tm) is obtained in the second cycle. The differential scanning calorimeter precision measurement (SSA) measurement is performed by heating and cooling to a temperature just before the peak of the melting temperature (Tm) after the first cycle using a differential scanning calorimeter (DSC), and then lowering the temperature by about 5°C. It is a method of obtaining more precise decision information by repeatedly performing heating and cooling processes (Eur. Polym. J. 2015, 65, 132).

When a small amount of the highly crystalline region is introduced into the olefin-based polymer, it does not appear when measuring the melting temperature using a general differential scanning calorimeter (DSC), and the high-temperature melting peak can be measured through the differential scanning calorimeter precision measurement method (SSA).

When the olefin-based polymer is measured by differential scanning calorimetry (SSA), a high-temperature melting peak is identified in the temperature range, and at this time, the melting enthalpy ΔH (75) of the corresponding region satisfies the above range, so that a conventional olefin-based polymer Compared with, when it has the same density and melt index values, it can have higher mechanical stiffness.

Meanwhile, the olefin-based polymer may additionally satisfy the requirement of (4) having a density (d) of 0.850 g/cc to 0.890 g/cc, and specifically, the density may be 0.850 g/cc to 0.880 g/cc, and , More specifically, it may be 0.860 g/cc to 0.875 g/cc.

In general, the density of the olefin-based polymer is affected by the type and content of monomers used in polymerization, the degree of polymerization, and the like, and in the case of a copolymer, the content of comonomers is greatly influenced. The olefin-based polymer included in the polypropylene-based composite material of the present invention is polymerized using a catalyst composition containing a transition metal compound having a characteristic structure, and a large amount of comonomer can be introduced. Can have.

In addition, the olefin-based polymer may further satisfy the requirement of (5) a weight average molecular weight (Mw) of 10,000 g/mol to 500,000 g/mol, and specifically, the weight average molecular weight (Mw) of 30,000 g/mol to It may be 300,000 g/mol, more specifically 50,000 g/mol to 200,000 g/mol. In the present invention, the weight average molecular weight (Mw) is a molecular weight in terms of polystyrene analyzed by gel permeation chromatography (GPC).

In addition, the olefin-based polymer may additionally satisfy the requirement of (6) Molecular Weight Distribution (MWD) of 0.1 to 6.0, which is the ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn). And, the molecular weight distribution (MWD) may be specifically 1.0 to 4.0, more specifically 2.0 to 3.0.

The olefin-based polymer is an olefin-based monomer, specifically an alpha-olefin-based monomer, a cyclic olefin-based monomer, a diene olefin-based monomer, a triene olefin-based monomer, and a styrene-based monomer, or any one homopolymer or two It may be a copolymer of the above. More specifically, the olefin-based polymer may be a copolymer of ethylene and an alpha-olefin having 3 to 12 carbon atoms or a copolymer of an alpha-olefin having 3 to 10 carbon atoms.

The alpha-olefin comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene , 1-tetradecene, 1-hexadecene, 1-itocene, norbornene, nobonadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4-butadiene, 1,5 -Pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene may contain any one or a mixture of two or more selected from the group consisting of styrene.

More specifically, the olefin-based polymer may be ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 4-methyl-1-pentene, or a copolymer of ethylene and 1-octene, and more specifically As such, the olefin-based polymer may be a copolymer of ethylene and 1-butene.

When the olefin-based polymer is a copolymer of ethylene and an alpha-olefin, the amount of the alpha-olefin is 90% by weight or less, more specifically 70% by weight or less, and even more specifically 5% to 60% by weight based on the total weight of the copolymer. It may be weight %, and more specifically, it may be 20 weight% to 50 weight %. When the alpha-olefin is included in the above range, it is easy to implement the above-described physical properties.

The olefin-based polymer included in the polypropylene-based composite material according to an embodiment of the present invention having the above physical properties and constitutional characteristics is in the presence of a metallocene catalyst composition containing at least one transition metal compound in a single reactor. It can be prepared through a continuous solution polymerization reaction in which hydrogen gas is added and the olefinic monomer is polymerized. Accordingly, in the olefin-based polymer included in the polypropylene-based composite according to an embodiment of the present invention, a block composed of two or more repeating units derived from any one of the monomers constituting the polymer in the polymer is connected in a linear manner is not formed. . That is, the olefin-based polymer contained in the polypropylene-based composite according to the present invention does not contain a block copolymer, and is a random copolymer, an alternating copolymer, and a graft copolymer. copolymer) may be selected from the group consisting of, and more specifically, may be a random copolymer.

In an example of the present invention, the amount of the hydrogen gas added may be 0.35 to 3 parts by weight, specifically 0.4 to 2 parts by weight, and more specifically 0.45 to 1.5 parts by weight based on 1 part by weight of the olefinic monomer introduced into the reaction system. It can be wealth. In addition, in an example of the present invention, when the olefin-based polymer is polymerized by continuous solution polymerization, the hydrogen gas is 0.35 to 3 kg/h, specifically 0.4 with respect to 1 kg/h of the olefin-based monomer introduced into the reaction system. To 2 kg/h, more specifically 0.45 to 1.5 kg/h.

Further, in another example of the present invention, when the olefin-based polymer is a copolymer of ethylene and an alpha-olefin, the hydrogen gas is 0.8 to 3 parts by weight, specifically 0.9 to 2.8 parts by weight, based on 1 part by weight of ethylene, More specifically, it may be added in an amount of 1 to 2.7 parts by weight. In addition, in an example of the present invention, when the olefin-based polymer is a copolymer of ethylene and an alpha-olefin, and is polymerized by continuous solution polymerization, the hydrogen gas is 0.8 to 1 kg/h of ethylene introduced into the reaction system. It may be added in an amount of 3 kg/h, specifically 0.9 to 2.8 kg/h, and more specifically 1 to 2.7 kg/h.

When polymerization is carried out under conditions in which the hydrogen gas is added in the above range, the olefin-based polymer of the present invention may satisfy the above-described physical properties.

Specifically, the olefin-based copolymer contained in the polypropylene-based composite material of the present invention is a step of polymerizing an olefin-based monomer by introducing hydrogen gas in the presence of a catalyst composition for olefin polymerization containing a transition metal compound of Formula 1 below. It can be obtained by a manufacturing method comprising a.

However, in the preparation of the olefin-based polymer according to an embodiment of the present invention, the range of the structure of the transition metal compound of Formula 1 is not limited to a specific disclosed form, and all included in the spirit and scope of the present invention It should be understood to include modifications, equivalents or substitutes.

[Formula 1]

In Formula 1,

R ₁ is the same as or different from each other, and each independently of a Group 4 metal substituted with hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl, silyl, alkylaryl, arylalkyl, or hydrocarbyl A metalloid radical, wherein the two R ₁ may be linked to each other by an alkylidine radical including an alkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms to form a ring;

R ₂ are the same as or different from each other, and each independently hydrogen; halogen; Alkyl of 1 to 20 carbon atoms; Aryl; Alkoxy; Aryloxy; An amido radical, and _{two or more of R 2} may be linked to each other to form an aliphatic ring or an aromatic ring;

R ₃ is the same as or different from each other, and each independently hydrogen; halogen; Alkyl of 1 to 20 carbon atoms; Or an aliphatic or aromatic ring including nitrogen, substituted or unsubstituted with an aryl radical, and when the number of the substituents is plural, two or more substituents among the substituents may be linked to each other to form an aliphatic or aromatic ring;

M is a Group 4 transition metal;

Q ₁ and Q ₂ are each independently halogen; Alkyl of 1 to 20 carbon atoms; Alkenyl; Aryl; Alkylaryl; Arylalkyl; Alkyl amido having 1 to 20 carbon atoms; Aryl amido; Or an alkylidene radical having 1 to 20 carbon atoms.

Further, in another example of the present invention, in Formula 1, R ₁ and R ₂ are the same as or different from each other, and each independently hydrogen; Alkyl of 1 to 20 carbon atoms; Aryl; Or it may be silyl,

R ₃ is the same as or different from each other, and alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl; Alkylaryl; Arylalkyl; Alkoxy having 1 to 20 carbon atoms; Aryloxy; Or may be amido; Wherein R ₆ in at least two R ₆ are connected to each other can form a aliphatic or aromatic ring;

The Q ₁ and Q ₂ are the same as or different from each other, and each independently halogen; Alkyl of 1 to 20 carbon atoms; Alkylamidos having 1 to 20 carbon atoms; May be an arylamido,

M may be a Group 4 transition metal.

The transition metal compound represented by Chemical Formula 1 has a narrow Cp-MN angle structurally because the metal sites are linked by a cyclopentadienyl ligand into which tetrahydroquinoline is introduced, and the monomer approaches Q ₁ -MQ ₂ (Q ₃ -MQ ₄ ) The angle has the feature of keeping it wide. In addition, Cp, tetrahydroquinoline, nitrogen and metal sites are sequentially connected by a cyclic bond to form a more stable and rigid pentagonal ring structure. Therefore, when these compounds are _{activated by reacting with a cocatalyst such as methylaluminoxane or B(C 6} F ₅ ) ₃ and then applied to olefin polymerization, characteristics such as high activity, high molecular weight and high co-polymerization are achieved even at high polymerization temperatures. It is possible to polymerize the possessed olefin-based polymer.

Each of the substituents defined in the present specification will be described in detail as follows.

The term'hydrocarbyl group' as used herein, unless otherwise stated, is a carbon number consisting only of carbon and hydrogen regardless of its structure, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl or arylalkyl. It means a monovalent hydrocarbon group of 1 to 20.

The term'halogen' as used herein means fluorine, chlorine, bromine or iodine unless otherwise stated.

The term'alkyl' as used herein, unless otherwise stated, means a straight or branched chain hydrocarbon moiety.

The term'cycloalkyl' as used herein refers to cyclic alkyl including cyclopropyl and the like unless otherwise stated.

The term “alkenyl” as used herein refers to a linear or branched alkenyl group unless otherwise stated.

The branched chain is an alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl of 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms.

The term'aryl' as used herein refers to an aromatic group having 6 to 20 carbon atoms unless otherwise stated, and specifically, phenyl, naphthyl, anthryl, phenanthryl, chrysenyl, pyrenyl, anthracenyl, pyridyl, dimethyl Anilinyl, anisolyl, and the like, but are not limited thereto.

The alkylaryl group means an aryl group substituted by the alkyl group.

The arylalkyl group refers to an alkyl group substituted by the aryl group.

The ring (or heterocyclic group) refers to a monovalent aliphatic or aromatic hydrocarbon group having 5 to 20 ring atoms and including one or more hetero atoms, and may be a single ring or a condensed ring of two or more rings. In addition, the heterocyclic group may or may not be substituted with an alkyl group. Examples of these include indoline, tetrahydroquinoline, and the like, but the present invention is not limited thereto.

The alkyl amino group refers to an amino group substituted by the alkyl group, and includes a dimethylamino group and a diethylamino group, but is not limited thereto.

According to an embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but are limited to these examples. no.

In the present specification, silyl may be silyl substituted or unsubstituted with alkyl having 1 to 20 carbon atoms, such as silyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl , Triisobutylsilyl, triethoxysilyl, triphenylsilyl, tris(trimethylsilyl)silyl, and the like, but are not limited thereto.

The compound of Formula 1 may be the following Formula 1-1, but is not limited thereto.

[Formula 1-1]

In addition, it may be a compound having various structures within the range defined in Chemical Formula 1.

Since the transition metal compound of Formula 1 can introduce a large amount of alpha-olefin as well as low-density polyethylene due to the structural characteristics of the catalyst, it is possible to prepare a low-density polyolefin copolymer at a level of 0.850 g/cc to 0.890 g/cc. .

The transition metal compound of Formula 1 may be prepared by the following method as an example.

[Scheme 1]

In Reaction Scheme 1, R ₁ to R ₃ , M, Q ₁ and Q ₂ are as defined in Formula 1.

Formula 1 may be prepared according to the method described in Patent Publication No. 2007-0003071, and the contents of the patent document are all included in the present specification.

The transition metal compound of Formula 1 may be used as a catalyst for a polymerization reaction in the form of a composition further comprising at least one of the cocatalyst compounds represented by Formula 2, Formula 3, and Formula 4 below.

[Formula 2]

_{- [Al (R 4) -O} ] a -

[Formula 3]

A(R ₄ ) ₃

[Formula 4]

^{[LH] + [W (D} ) 4] - or ^{[L] + [W (D} ) 4] -

In Formulas 2 to 3,

R ₄ may be the same as or different from each other, and each independently selected from the group consisting of halogen, hydrocarbyl having 1 to 20 carbon atoms, and hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,

A is aluminum or boron,

D is each independently aryl having 6 to 20 carbon atoms or alkyl having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, wherein the substituent is halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms And at least one selected from the group consisting of aryloxy having 6 to 20 carbon atoms,

H is a hydrogen atom,

L is a neutral or cationic Lewis base,

W is a group 13 element,

a is an integer of 2 or more.

Examples of the compound represented by Formula 2 include alkyl aluminoxanes such as methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane, and two or more of the alkyl aluminoxanes are mixed. And modified alkylaluminoxane, specifically methylaluminoxane, and modified methylaluminoxane (MMAO).

Examples of the compound represented by Formula 3 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl Boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, etc. are included, and specifically, may be selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.

Examples of the compound represented by Chemical Formula 4 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra (o,p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenyl boron, N,N -Diethylanilinium tetraphenyl boron, N,N-diethylanilinium tetrapentafluorophenyl boron, diethyl ammonium tetrapentafluorophenyl boron, triphenylphosphonium tetraphenyl boron, trimethylphosphonium tetraphenyl boron, dimethyl Anilinium tetrakis (pentafluorophenyl) borate, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tri Propyl ammonium tetra (p-tolyl) aluminum, triethyl ammonium tetra (o,p-dimethylphenyl) aluminum, tributyl ammonium tetra (p-trifluoromethylphenyl) aluminum, trimethyl ammonium tetra (p-trifluoromethylphenyl) aluminum , Tributylammonium tetrapentafluorophenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentafluorophenylaluminum, triphenyl Phosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropyl ammonium tetra (p-tolyl) boron, triethyl ammonium tetra (o,p-dimethylphenyl) boron, triphenylcarbonium tetra (p-trifluoromethylphenyl) ) Boron or triphenylcarbonium tetrapentafluorophenyl boron, and the like.

The catalyst composition, as a first method, comprises: 1) contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 2 or Formula 3 to obtain a mixture; And 2) adding the compound represented by Formula 4 to the mixture.

In addition, the catalyst composition may be prepared by contacting the compound represented by Formula 4 with the transition metal compound represented by Formula 1 as a second method.

In the case of the first method of manufacturing the catalyst composition, the molar ratio of the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2/the compound represented by Formula 2 or Formula 3 is 1/ It may be 5,000 to 1/2, specifically 1/1,000 to 1/10, and more specifically 1/500 to 1/20. When the molar ratio of the transition metal compound represented by Formula 1/the compound represented by Formula 2 or Formula 3 exceeds 1/2, the amount of the alkylating agent is very small, and there is a problem that the alkylation of the metal compound does not proceed completely. , When the molar ratio is less than 1/5,000, the alkylation of the metal compound is performed, but there is a problem that the activation of the alkylated metal compound is not completely achieved due to a side reaction between the remaining excess alkylating agent and the activator, which is a compound of Formula 4. . In addition, the molar ratio of the transition metal compound represented by Formula 1 / the compound represented by Formula 4 may be 1/25 to 1, specifically 1/10 to 1, and more specifically 1/5 to May be 1. When the molar ratio of the transition metal compound represented by Chemical Formula 1 / the compound represented by Chemical Formula 4 exceeds 1, the amount of the activator is relatively small, and thus the activation of the metal compound is not completely performed, and thus the activity of the resulting catalyst composition When the molar ratio is less than 1/25, activation of the metal compound is completely achieved, but the unit cost of the catalyst composition may not be economical or the purity of the resulting polymer may be reduced with an excess amount of the remaining activator.

In the case of the second method of the method for preparing the catalyst composition, the molar ratio of the transition metal compound represented by Chemical Formula 1 / the compound represented by Chemical Formula 4 may be 1/10,000 to 1/10, and specifically 1/5,000 It may be to 1/100, and more specifically, it may be 1/3,000 to 1/500. When the molar ratio exceeds 1/10, the amount of the activator is relatively small, so that the activation of the metal compound may not be completed, and thus the activity of the resulting catalyst composition may decrease, and when it is less than 1/10,000, the activation of the metal compound. Is completely achieved, but the unit cost of the catalyst composition may not be economical or the purity of the resulting polymer may be degraded with an excess amount of activator remaining.

When preparing the catalyst composition, a hydrocarbon solvent such as pentane, hexane, or heptane, or an aromatic solvent such as benzene or toluene may be used as the reaction solvent.

In addition, the catalyst composition may include the transition metal compound and the cocatalyst compound in a form supported on a carrier.

The carrier may be used without particular limitation as long as it is used as a carrier in a metallocene catalyst. Specifically, the carrier may be silica, silica-alumina or silica-magnesia, and any one or a mixture of two or more of them may be used.

Among these, when the carrier is silica, since the functional groups of the silica carrier and the metallocene compound of Formula 1 chemically form bonds, there is hardly any catalyst released from the surface during the olefin polymerization process. As a result, it is possible to prevent the occurrence of fouling in which the reactor wall or polymer particles are entangled during the production process of the olefin-based polymer. In addition, the olefin-based polymer prepared in the presence of a catalyst including the silica carrier has excellent particle shape and apparent density of the polymer.

More specifically, the carrier may be high-temperature dried silica or silica-alumina including a highly reactive siloxane group on the surface through a method such as high-temperature drying.

The carrier may further include an oxide, carbonate, sulfate or nitrate component such as _{Na 2} O, K ₂ CO ₃ , BaSO ₄ or Mg(NO ₃ ) _2.

The polymerization reaction for polymerizing the olefinic monomer may be performed by a conventional process applied to polymerization of the olefin monomer, such as continuous solution polymerization, bulk polymerization, suspension polymerization, slurry polymerization, or emulsion polymerization.

The polymerization reaction of the olefin monomer may be performed under an inert solvent, and examples of the inert solvent include benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene may be mentioned, but is not limited thereto.

The polymerization of the olefin-based polymer may be performed at a temperature of about 25°C to about 500°C, specifically 80°C to 250°C, more preferably 100°C to 200°C. In addition, the reaction pressure during polymerization is 1 kgf/cm ² to 150 kgf/cm ² , preferably 1 kgf/cm ² to 120 kgf/cm ² , more preferably 5 kgf/cm ² to 100 kgf/cm ² Can be

Example

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

Catalyst Preparation Example 1: Preparation of transition metal compound A

(1) 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline (8-(2,3,4,5- Preparation of Tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline)

(i) Preparation of lithium carbamate

1,2,3,4-tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150 mL) were added to a Schlenk flask. The Schlenk flask was immersed in a -78°C low temperature bath made of dry ice and acetone and stirred for 30 minutes. Then, n-BuLi (39.3 mL, 2.5 M, 98.24 mmol) was injected into a syringe under a nitrogen atmosphere, and a pale yellow slurry was formed. Then, after the flask was stirred for 2 hours, the temperature of the flask was raised to room temperature while removing the generated butane gas. The flask was again immersed in a -78°C low temperature bath to lower the temperature, and then CO ₂ gas was added. As the carbon dioxide gas was added, the slurry disappeared, resulting in a transparent solution. The flask was connected to a bubbler and the temperature was raised to room temperature while removing carbon dioxide gas. After that, excess CO ₂ gas and solvent were removed under vacuum. After the flask was transferred to a dry box, pentane was added, stirred vigorously, and filtered to obtain a white solid compound, lithium carbamate. The white solid compound is coordinated with diethyl ether. At this time, the yield is 100%.

¹ H NMR(C ₆ D ₆ , C ₅ D ₅ N): δ 1.90 (t, J = 7.2 Hz, 6H, ether), 1.50 (br s, 2H, quin-CH ₂ ), 2.34 (br s, 2H , quin-CH ₂ ), 3.25 (q, J = 7.2 Hz, 4H, ether), 3.87 (br, s, 2H, quin-CH ₂ ), 6.76 (br d, J = 5.6 Hz, 1H, quin-CH ) ppm

¹³ C NMR (C ₆ D ₆ ): δ 24.24, 28.54, 45.37, 65.95, 121.17, 125.34, 125.57, 142.04, 163.09 (C=O) ppm

(ii) Preparation of 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline

The lithium carbamate compound (8.47 g, 42.60 mmol) prepared in step (i) was added to a Schlenk flask. Then, tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were sequentially added. The Schlenk flask was immersed in a -20°C low temperature bath made of acetone and a small amount of dry ice, stirred for 30 minutes, and then t-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added. At this time, the color of the reaction mixture turned red. The mixture was stirred for 6 hours while maintaining -20°C. CeCl ₃ · 2LiCl solution (129 mL, 0.33 M, 42.60 mmol) dissolved in tetrahydrofuran and tetramethylcyclopentinone (5.89 g, 42.60 mmol) were mixed in a syringe, and then introduced into a flask under a nitrogen atmosphere. The temperature of the flask was slowly raised to room temperature, and after 1 hour, the thermostat was removed and the temperature was maintained at room temperature. Then, after adding water (15 mL) to the flask, ethyl acetate was added thereto, followed by filtration to obtain a filtrate. After transferring the filtrate to a separatory funnel, hydrochloric acid (2 N, 80 mL) was added and shaken for 12 minutes. Then, after neutralization by adding a saturated aqueous sodium hydrogen carbonate solution (160 mL), the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer to remove moisture and then filtered, the filtrate was taken and the solvent was removed. The obtained filtrate was purified by column chromatography using hexane and ethyl acetate (v/v, 10:1) solvent to obtain a yellow oil. The yield was 40%.

¹ H NMR (C ₆ D ₆ ): δ 1.00 (br d, 3H, Cp-CH ₃ ), 1.63-1.73 (m, 2H, quin-CH ₂ ), 1.80 (s, 3H, Cp-CH ₃ ), 1.81 (s, 3H, Cp-CH ₃ ), 1.85 (s, 3H, Cp-CH ₃ ), 2.64 (t, J = 6.0 Hz, 2H, quin-CH ₂ ), 2.84-2.90 (br, 2H, quin -CH ₂ ), 3.06 (br s, 1H, Cp-H), 3.76 (br s, 1H, NH), 6.77 (t, J = 7.2 Hz, 1H, quin-CH), 6.92 (d, J = 2.4 Hz, 1H, quin-CH), 6.94 (d, J = 2.4 Hz, 1H, quin-CH) ppm

(2) [(1,2,3,4-tetrahydroquinoline-8-yl)tetramethylcyclopentadienyl- η ⁵ , κ Preparation of -N] titanium dimethyl ([(1,2,3,4-Tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-eta5,kapa-N]titanium dimethyl)

(i) [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- η ⁵ , κ -N] Preparation of dilithium compound

8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline (8.07 g) prepared through step (1) in a dry box , 32.0 mmol) and 140 mL of diethyl ether were added to a round flask, and the temperature was lowered to -30°C, and n-BuLi (17.7 g, 2.5 M, 64.0 mmol) was slowly added while stirring. It was reacted for 6 hours while raising the temperature to room temperature. After that, it was filtered while washing several times with diethyl ether, and a solid was obtained. Vacuum was applied to remove the remaining solvent to obtain a yellow solid dilithium compound (9.83 g). The yield was 95%.

¹ H NMR(C ₆ D ₆ , C ₅ D ₅ N): δ 2.38 (br s, 2H, quin-CH ₂ ), 2.53 (br s, 12H, Cp-CH ₃ ), 3.48 (br s, 2H, quin-CH ₂ ), 4.19 (br s, 2H, quin-CH ₂ ), 6.77 (t, J = 6.8 Hz, 2H, quin-CH), 7.28 (br s, 1H, quin-CH), 7.75 (brs , 1H, quin-CH) ppm

(ii) Preparation of (1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- η ⁵ , κ- N] titanium dimethyl

In a dry box, TiCl ₄ ·DME (4.41 g, 15.76 mmol) and diethyl ether (150 mL) were placed in a round flask, and MeLi (21.7 mL, 31.52 mmol, 1.4 M) was slowly added while stirring at -30°C. After stirring for 15 minutes, the [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- ηη ⁵ , κ- N]dilithium compound prepared in step (i) ( 5.30 g, 15.76 mmol) was added to the flask. The mixture was stirred for 3 hours while raising the temperature to room temperature. After the reaction was completed, vacuum was applied to remove the solvent, dissolved in pentane, and filtered to obtain a filtrate. When pentane was removed by applying vacuum, a dark brown compound (3.70 g) was obtained. The yield was 71.3%.

¹ H NMR(C ₆ D ₆ ): δ 0.59 (s, 6H, Ti-CH ₃ ), 1.66 (s, 6H, Cp-CH ₃ ), 1.69 (br t, J = 6.4 Hz, 2H, quin-CH ₂ ), 2.05 (s, 6H, Cp-CH ₃ ), 2.47 (t, J = 6.0 Hz, 2H, quin-CH ₂ ), 4.53 (m, 2H, quin-CH ₂ ), 6.84 (t, J = 7.2 Hz, 1H, quin-CH), 6.93 (d, J =7.6 Hz, quin-CH), 7.01 (d, J =6.8 Hz, quin-CH) ppm

¹³ C NMR (C ₆ D ₆ ): δ 12.12, 23.08, 27.30, 48.84, 51.01, 119.70, 119.96, 120.95, 126.99, 128.73, 131.67, 136.21 ppm

Catalyst Preparation Example 2: Preparation of transition metal compound B

(1) Preparation of 2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline

Except for using 2-methyl indoline in place of 1,2,3,4-tetrahydroquinoline in (1) of Preparation Example 1, 2 -Methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline was prepared. The yield was 19%.

¹ H NMR (C ₆ D ₆ ): δ 6.97 (d, J=7.2Hz, 1H, CH), δ 6.78 (d, J=8Hz, 1H, CH), δ 6.67 (t, J=7.4Hz, 1H , CH), δ 3.94 (m, 1H, quinoline-CH), δ 3.51 (br s, 1H, NH), δ 3.24-3.08 (m, 2H, quinoline-CH ₂ , Cp-CH), δ 2.65 (m , 1H, quinoline-CH ² ), δ 1.89 (s, 3H, Cp-CH ₃ ), δ 1.84 (s, 3H, Cp-CH ₃ ), δ 1.82 (s, 3H, Cp-CH ₃ ), δ 1.13 (d, J=6Hz, 3H, quinoline-CH ₃ ), δ 0.93 (3H, Cp-CH ₃ ) ppm.

(2) [(2-methylindolin-7-yl)tetramethylcyclopentadienyl-ethane5, kappa-N] titanium dimethyl ([(2-Methylindolin-7-yl)tetramethylcyclopentadienyl-eta5,kapa-N] titanium dimethyl)

(i) 2-methyl-7-(2,3 in place of 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline ,4,5-tetramethyl-1,3-cyclopentadienyl)-indoline (2.25 g, 8.88 mmol) was used in the same manner as in Preparation Example 1 (2) (i) A dilithium salt compound (compound 4 g) coordinated with 0.58 equivalent of diethyl ether was obtained (1.37 g, 50%).

¹ H NMR (Pyridine-d8): δ 7.22 (br s, 1H, CH), δ 7.18 (d, J=6Hz, 1H, CH), δ 6.32 (t, 1H, CH), δ 4.61 (brs, 1H) , CH), δ 3.54 (m, 1H, CH), δ 3.00 (m, 1H, CH), δ 2.35-2.12 (m ,13H, CH, Cp-CH3), δ 1.39 (d, indoline-CH3) ppm .

(ii) A titanium compound was prepared using the dilithium salt compound (compound 4 g) (1.37 g, 4.44 mmol) prepared in (i) above in the same manner as in (2)(ii) of Preparation Example 1.

¹ H NMR (C ₆ D ₆ ): δ 7.01-6.96 (m, 2H, CH), δ 6.82 (t, J=7.4Hz, 1H, CH), δ

4.96 (m, 1H, CH), δ 2.88 (m, 1H, CH), δ 2.40 (m, 1H, CH), δ 2.02 (s, 3H, Cp-CH ₃ ), δ 2.01 (s, 3H, Cp -CH ₃ ), δ 1.70 (s, 3H, Cp-CH ₃ ), δ 1.69 (s, 3H, Cp-CH ₃ ), δ 1.65 (d, J=6.4Hz, 3H, indoline-CH ₃ ), δ 0.71 (d, J=10 Hz, 6H, TiMe ₂ -CH ₃ ) ppm.

Example Preparation Example 1

After filling a 1.5 L continuous process reactor with hexane solvent (5 kg/h) and 1-butene (0.95 kg/h), the temperature at the top of the reactor was preheated to 140.7°C. Triisobutylaluminum compound (0.06 mmol/min), transition metal compound B (0.40 μmol/min) obtained in Catalyst Preparation Example 2, and dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (1.20 μmol/min) ) Was introduced into the reactor at the same time. Subsequently, hydrogen gas (15 cc/min) and ethylene (0.87 kg/h) were introduced into the reactor and maintained at 141° C. for 30 minutes or more in a continuous process at a pressure of 89 bar to proceed with a copolymerization reaction to obtain a copolymer. . After drying for 12 hours or more in a vacuum oven, the physical properties were measured.

Examples Preparation Examples 2 to 5

Example The copolymerization reaction was carried out in the same manner as in Preparation Example 1, and the amount of the transition metal compound, the amount of catalyst and cocatalyst, and the reaction temperature, the amount of hydrogen input, and the amount of comonomer were changed as shown in Table 1 below to carry out the copolymerization reaction. A copolymer was obtained.

Comparative Preparation Example 1

Mitsui Chemicals DF610 was purchased and used.

Comparative Preparation Examples 2 to 4

Example The copolymerization reaction was carried out in the same manner as in Preparation Example 1, and the types of the transition metal compound, the amount of the transition metal compound, the amount of the catalyst and the cocatalyst, and the reaction temperature, the amount of hydrogen input, and the amount of comonomer were respectively shown in Table 1 below. It changed and the copolymerization reaction proceeded to obtain a copolymer.

Comparative Preparation Example 5

Mitsui Chemicals DF710 was purchased and used.

Comparative Production Example 6

Mitsui Chemical's DF640 was purchased and used.

Comparative Production Example 7

Dow's EG7447 was purchased and used.

	Catalyst type	catalyst usage (μmol /min)	Cocatalyst (μmol /min)	TiBAl (mmol /min)	Ethylene (kg/h)	Hexane (Kg/h)	1-butene (kg/h)	Hydrogen (cc/min)	Reaction temperature (℃
Example Preparation Example 1	Transition metal compound B	0.40	1.20	0.06	0.87	5	0.95	15	141
Example Preparation 2	Transition metal compound B	0.60	1.80	0.05	0.87	7	0.93	32	145
Example Preparation 3	Transition metal compound B	0.45	1.35	0.04	0.87	7	0.75	15	145
Example Preparation Example 4	Transition metal compound B	0.74	2.22	0.05	0.87	7	0.93	25	150
Example Preparation 5	Transition metal compound B	0.55	1.65	0.04	0.87	7	0.84	38	148
Comparative Preparation Example 2	Transition metal compound B	0.78	2.34	0.06	0.87	5	1.15	-	161
Comparative Preparation Example 3	Transition metal compound A	0.32	0.96	0.05	0.87	5	0.62	-	145
Comparative Preparation Example 4	Transition metal compound B	0.50	1.50	0.06	0.87	5	1.15	10	161
Additional Comparative Preparation Example 8								Overuse

Experimental Example 1: Evaluation of physical properties of olefin-based polymers The copolymers of Preparation Examples 1 to 5 and Comparative Preparation Examples 1 to 4 were evaluated according to the following method, and are shown in Tables 2 and 3 below.

1) Density of polymer

Measured by ASTM D-792.

2) Polymer melt index (MI)

It was measured by ASTM D-1238 (Condition E, 190°C, 2.16 Kg load).

3) Weight average molecular weight (Mw, g/mol) and molecular weight distribution (MWD)

The number average molecular weight (Mn) and the weight average molecular weight (Mw) were respectively measured using gel permeation chromatography (GPC), and the molecular weight distribution was calculated by dividing the weight average molecular weight by the number average molecular weight.

-Column: PL Olexis

-Solvent: Trichlorobenzene (TCB)

-Flow rate: 1.0 ml/min

-Sample concentration: 1.0 mg/ml

-Injection volume: 200 µl

-Column temperature: 160℃

-Detector: Agilent High Temperature RI detector

-Standard: Polystyrene (corrected by 3rd order function)

4) Melting point of polymer (Tm)

It was obtained using a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 250) manufactured by TA instrument. That is, after increasing the temperature to 150° C., the temperature was maintained at that temperature for 1 minute, then decreased to -100° C., and the temperature was increased again to set the top of the DSC curve as the melting point. At this time, the rate of temperature rise and fall is 10°C/min, and the melting point is obtained while the second temperature rises.

FIG. 1 shows a DSC graph of the polymer of Example Preparation Example 1, and FIG. 2 shows a DSC graph of the polymer of Comparative Preparation Example 1, respectively.

5) High-temperature melting peak of polymer and total enthalpy of melting above 75℃ Δ H(75)

It was obtained by using a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 250) manufactured by TA instrument using SSA (Successive self-nucleation/annealing) measurement method.

Specifically, after increasing the temperature to 150°C in the first cycle, it was kept at that temperature for 1 minute and then cooled to -100°C. In the second cycle the temperature was increased to 120° C., then held at that temperature for 30 minutes and then cooled to -100° C. In the third cycle, the temperature was increased to 110° C., then held at that temperature for 30 minutes and then cooled to -100° C. In this way, the process of raising the temperature at intervals of 10° C. and cooling to -100° C. was repeated up to -60° C. to achieve crystallization for each temperature section.

The heat capacity was specified while increasing the temperature to 150° C. in the last cycle. Thereafter, the enthalpy of melting at 75°C or higher was summed to obtain ΔH (75).

Fig. 3 shows the SSA graph of the polymer of Example Preparation Example 1, and Fig. 4 shows the SSA graph of the polymer of Comparative Preparation Example 1, respectively.

6) Hardness (shore A)

The hardness was measured according to ASTM D2240 standard using TECLOCK's GC610 STAND for Durometer and Mitutoyo's Shore hardness tester Type A.

7) Tensile strength and tear strength of polymer

The olefin-based copolymers of Preparation Example 1 and Comparative Preparation Examples 1 to 3 were each extruded into pellets, and then the tensile strength and tear strength at the time of bankruptcy were measured according to ASTM D638 (50 mm/min).

	density (g/mL)	MI (g/10min)	Mw (g/mol)	MWD	DSC	SSA
					Tm (℃)	Presence of hot melting peak	ΔH(75) (J/g)
Example Preparation Example 1	0.862	1.20	106,000	2.01	32.1	has exist	1.04
Example Preparation 2	0.866	4.39	69,070	2.07	33.0	has exist	1.61
Example Preparation 3	0.872	1.22	99,068	2.05	45.9	has exist	1.11
Example Preparation Example 4	0.866	3.30	70,000	2.11	37.8	has exist	1.05
Example Preparation 5	0.865	5.10	75,388	2.09	37.2	has exist	1.12
Comparative Preparation Example 1	0.861	1.32	105,000	1.98	39.7	none	0
Comparative Preparation Example 2	0.861	1.12	102,000	2.11	28.6	has exist	0.71
Comparative Preparation Example 3	0.862	1.20	91,419	2.18	28.5	has exist	0.56
Comparative Preparation Example 4	0.862	1.23	100,423	2.185	29.9	has exist	0.61
Comparative Preparation Example 5	0.869	1.20	92,000	2.04	49.3	none	0
Comparative Production Example 6	0.865	3.40	71,000	2.04	43.8	none	0
Comparative Production Example 7	0.868	5.10	76,735	2.14	44.2	none	0.48
Additional Comparative Preparation Example 8

	density (g/mL)	MI (g/10min)	MWD	DSC	SSA	The tensile strength	Tear strength	Hardness (Shore A)
				Tm (℃)	ΔH(75) (J/g)
Example Preparation Example 1	0.862	1.20	2.01	32.1	1.04	2.2	29.5	55.0
Comparative Preparation Example 1	0.861	1.32	1.98	39.7	0	2.1	25.6	56.7
Comparative Preparation Example 2	0.861	1.12	2.11	28.6	0.71	1.6	22.4	52.9
Comparative Preparation Example 3	0.862	1.20	2.18	28.5	0.56	1.3	16.7	51.6

When comparing the olefin-based polymer of Example 1 and the olefin-based polymer of Comparative Preparation 1 having the same density and MI, Figs. 1 and 2 measured by DSC show similar trends and show similar graph forms, showing a large difference. Although not confirmed, it can be seen that there is a large difference in the high temperature region of 75° C. or higher in FIGS. 3 and 4 measured by SSA. Specifically, in Preparation Example 1, the peak appears at 75°C or higher, whereas the Comparative Preparation Example does not appear. Comparative Preparation Example 2 and Comparative Preparation Example 3 had a peak in the corresponding region, but the size was smaller than that of the Example Preparation Example. Due to the difference in the high-temperature melting peak measured by SSA, Example 1 had a ΔH (75) of 1.0. A value of J/g or more was shown, but in the comparative example, ΔH(75) was less than 1.0 J/g or there was no peak in the corresponding region.

Through Table 3, it is possible to compare the mechanical strength of Example Preparation Example 1 and Comparative Preparation Examples 1, 2, and 3 having the same density and MI. Example In Preparation Example 1, a polymer melted at a high temperature was introduced to increase mechanical stiffness, and thus it can be seen that tensile strength and tear strength were increased compared to Comparative Examples 1 to 3.

Examples Preparation Examples 1 to 5 are polymers obtained by polymerizing an olefin-based monomer while introducing hydrogen gas, and a high crystalline region was introduced to exhibit a high-temperature melting peak, and accordingly, ΔH (75) exhibited a value of 1.0 J/g or more. And showed high mechanical stiffness. Through the comparison with Comparative Preparation Example 2 and Comparative Preparation Example 4, whether or not ΔH (75) satisfies a value of 1.0 J/g or more varies depending on whether hydrogen gas is added and the amount of addition during polymerization, and mechanical stiffness is also changed. Was able to confirm.

Example 1: Preparation of polypropylene-based composite material

20 parts by weight of the olefin copolymer prepared in Example 1, 60 parts by weight of a highly crystalline impact copolymer polypropylene (CB5230, manufactured by Daehan Emulsifier) having a melt index (230° C., 2.16 kg) of 30 g/10 min, and 20 parts by weight of talc (KCNAP-400™, Kotsu Corporation) (average particle diameter (D ₅₀ ) = 11.0 µm) is added, and 0.1 parts by weight of AO1010 (Irganox 1010, Ciba Specialty Chemicals) as an antioxidant, tris (2,4-di -tert-butylphenyl)phosphite (A0168) 0.1 parts by weight and calcium stearate (Ca-st) 0.3 parts by weight are added, and then melt-kneaded using a twin screw extruder to obtain a pellet-shaped polypropylene composite compound. Was prepared. At this time, the twin-screw extruder had a diameter of 25 Φ, a diameter-length ratio of 40, a barrel temperature of 200°C to 230°C, a screw rotation speed of 250 rpm, and an extrusion amount of 25 kr/hr.

Examples 2 to 5: Preparation of polypropylene-based composite material

A polypropylene-based composite was manufactured in the same manner as in Example 1, except that the olefin copolymer as shown in Table 4 below was used in place of the olefin copolymer prepared in Preparation Example 1. At this time, in Example 5, the type of polypropylene and the ratio of the olefin copolymer and the polypropylene were different.

Polypropylene represented by CB5290 in Table 4 below is a highly crystalline impact copolymer polypropylene (CB5290, manufactured by Daehan Emulsifier) having a melt index (230°C, 2.16kg) of 90 g/10 min.

Comparative Examples 1 to 7: Preparation of polypropylene-based composite material

A polypropylene-based composite was manufactured in the same manner as in Example 1, except that the olefin copolymer as shown in Table 4 below was used in place of the olefin copolymer prepared in Preparation Example 1. At this time, in Comparative Example 7, the types of polypropylene and the ratio of the olefin copolymer and the polypropylene were different.

Polypropylene represented by CB5290 in Table 4 below is a highly crystalline impact copolymer polypropylene (CB5290, manufactured by Daehan Emulsifier) having a melt index (230°C, 2.16kg) of 90 g/10 min.

	Olefinic polymer	Polypropylene	Mixing ratio
			Olefin polymer (weight%)	PP (weight%)	Talc (weight%)
Example 1	Example Preparation Example 1	CB5230	20	60	20
Example 2	Example Preparation 3	CB5230	20	60	20
Example 3	Example Preparation Example 4	CB5230	20	60	20
Example 4	Example Preparation 5	CB5230	20	60	20
Example 5	Example Preparation 3	CB5290	30	50	20
Comparative Example 1	Comparative Preparation Example 1	CB5230	20	60	20
Comparative Example 2	Comparative Preparation Example 2	CB5230	20	60	20
Comparative Example 3	Comparative Preparation Example 3	CB5230	20	60	20
Comparative Example 4	Comparative Preparation Example 5	CB5230	20	60	20
Comparative Example 5	Comparative Production Example 6	CB5230	20	60	20
Comparative Example 6	Comparative Production Example 7	CB5230	20	60	20
Comparative Example 7	Comparative Preparation Example 5	CB5290	30	50	20

Experimental Example 2: Evaluation of physical properties of polypropylene composites

In order to confirm the physical properties of the polypropylene-based composites prepared in Examples 1 to 5 and Comparative Examples 1 to 7, the polypropylene-based composites were prepared by injection molding at a temperature of 230°C using an injection machine, and a constant temperature After standing in a humidity room for 1 day, the specific gravity of the polymer, the melt index of the polymer, tensile strength, flexural strength and flexural modulus, low and room temperature impact strength, and shrinkage were measured. The physical properties of the prepared specimens are shown in Table 5 below.

1) Specific gravity

Measured according to ASTM D792.

2) Polymer melt index (MI)

The melt index (MI) of the polymer was measured by ASTM D-1238 (Condition E, 230°C, 2.16 Kg load).

3) Tensile strength and flexural strength

Measurements were made according to ASTM D790 using an INSTRON 3365 apparatus.

4) Low and room temperature impact strength

It was performed according to ASTM D256, and the impact strength at room temperature was measured under the conditions of room temperature (23° C.), and the impact strength at low temperature was measured after standing in a low temperature chamber (-30° C.) for 12 hours or more.

	importance	MI (g/10min)	The tensile strength	Flexural strength	Low temperature impact strength	Room temperature impact strength
Example 1	1.033	14.3	211	341	4.7	42.1
Comparative Example 1	1.041	14.6	211	336	4.7	43.9
Comparative Example 2	1.030	13.9	206	334	4.8	42.5
Comparative Example 3	1.038	13.9	205	327	4.7	40.9
Example 2	1.037	14.6	219	344	3.6	34.5
Comparative Example 4	1.03	15.0	216	340	3.8	37.3
Example 3	1.032	17.0	239	336	3.8	34.8
Comparative Example 5	1.032	17.4	238	334	3.8	34.5
Example 4	1.036	17.7	217	336	4.3	32.9
Comparative Example 6	1.031	17.8	217	333	4.4	33.1
Example 5	1.031	16.2	171	246	8.4	53.7
Comparative Example 7	1.033	16.7	168	241	9.0	52.8

Referring to Table 5, when comparing polypropylene-based composites containing olefin-based copolymers having equivalent density and MI values, the polypropylene-based composite of the Example was at a similar level of low temperature compared to the polypropylene-based composite of Comparative Example It can be seen that mechanical strength such as tensile strength and flexural strength has been improved while maintaining the impact strength and room temperature impact strength. Through this, it was confirmed that the mechanical stiffness of the polypropylene-based composite material was increased by including an olefin-based copolymer exhibiting high mechanical stiffness due to the introduction of a high crystallinity region.

Claims (14)

1. (A) polypropylene, and

   (B) Polypropylene-based composite material containing an olefin-based polymer satisfying the following requirements (1) to (3):

   (1) the melt index (Melt Index, MI, 190°C, 2.16 kg load condition) is 0.1 g/10 min to 10.0 g/10 min,

   (2) When measuring a differential scanning calorimeter (DSC), the melting temperature is 20°C to 70°C,

   (3) When measuring the differential scanning calorimeter precision measurement method (SSA), a high-temperature melting peak is observed at 75°C to 150°C, and the total ΔH(75) of the melting enthalpy of the region is 1.0 J/g or more.
2. The method of claim 1,

   The (A) polypropylene is a polypropylene-based composite material having a melt index of 0.5 g/10min to 100 g/10min measured at 230°C and a load of 2.16 kg.
3. The method of claim 1,

   The (A) polypropylene is an impact copolymer having a melt index of 0.5 g/10min to 100 g/10min measured at 230°C and a load of 2.16 kg, a polypropylene-based composite.
4. The method of claim 1,

   The (B) olefin-based polymer further satisfies the requirement of (4) having a density (d) of 0.850 g/cc to 0.890 g/cc.
5. The method of claim 1,

   The (B) olefin-based polymer further satisfies the requirement of (5) a weight average molecular weight (Mw) of 10,000 g/mol to 500,000 g/mol.
6. The method of claim 1,

   The (B) olefin-based polymer further satisfies the requirement of (6) molecular weight distribution (MWD, molecular weight density) of 0.1 to 6.0.
7. The method of claim 1,

   The (B) olefin-based polymer is a polypropylene-based composite which is a copolymer of ethylene and an alpha-olefin comonomer having 3 to 12 carbon atoms.
8. The method of claim 7,

   The alpha-olefin comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene , 1-tetradecene, 1-hexadecene, 1-itocene, norbornene, nobonadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4-butadiene, 1,5 -Pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and a polypropylene-based composite comprising any one or a mixture of two or more selected from the group consisting of 3-chloromethylstyrene.
9. The method of claim 1,

   The (B) olefin-based polymer is a polypropylene-based composite material which is a copolymer of ethylene and 1-hexene.
10. The method of claim 1,

    The (B) olefin-based polymer is obtained by a production method comprising the step of polymerizing an olefin-based monomer by introducing hydrogen gas in the presence of a catalyst composition for olefin polymerization containing a transition metal compound of Formula 1 below. Propylene-based composite:

    [Formula 1]

    

    In Formula 1,

    R ₁ is the same as or different from each other, and each independently of a Group 4 metal substituted with hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl, silyl, alkylaryl, arylalkyl, or hydrocarbyl A metalloid radical, wherein the two R ₁ may be linked to each other by an alkylidine radical including an alkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms to form a ring;

    R ₂ are the same as or different from each other, and each independently hydrogen; halogen; Alkyl of 1 to 20 carbon atoms; Aryl; Alkoxy; Aryloxy; An amido radical, and _{two or more of R 2} may be linked to each other to form an aliphatic ring or an aromatic ring;

    R ₃ is the same as or different from each other, and each independently hydrogen; halogen; Alkyl of 1 to 20 carbon atoms; Or an aliphatic or aromatic ring including nitrogen, substituted or unsubstituted with an aryl radical, and when the number of the substituents is plural, two or more substituents among the substituents may be linked to each other to form an aliphatic or aromatic ring;

    M is a Group 4 transition metal;

    Q ₁ and Q ₂ are each independently halogen; Alkyl of 1 to 20 carbon atoms; Alkenyl; Aryl; Alkylaryl; Arylalkyl; Alkyl amido having 1 to 20 carbon atoms; Aryl amido; Or an alkylidene radical having 1 to 20 carbon atoms.
11. The method of claim 1,

    The (B) olefin-based polymer is prepared by a continuous solution polymerization reaction using a continuous stirred reactor (Continuous Stirred Tank Reactor) by introducing hydrogen gas in the presence of the catalyst composition for olefin polymerization, a polypropylene-based composite.
12. The method of claim 1,

    The polypropylene-based composite is a polypropylene-based composite comprising 5% to 40% by weight of the (B) olefin-based polymer.
13. The method of claim 1,

    The polypropylene-based composite material is a polypropylene-based composite material further comprising an inorganic filler.
14. The method of claim 13,

    The polypropylene-based composite material (A) contains the inorganic filler in an amount of 0.1 parts by weight to 40 parts by weight based on 100 parts by weight of polypropylene,

    The inorganic filler is a polypropylene-based composite material having an average particle diameter (D _{50) of 1 µm to 20 µm.}

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